O-pyrazolopyrimidine-(thiono)-phosphoric-(phosphonic or phosphinic)-acid esters or ester-amides

ABSTRACT

1. AN O-PYRAZOLOPYRIMIDINE - (THIONO) - PHOSPHORIC(PHOSPHONIC OR PHOSPINIC)-ACID ESTER OF THE FORMULA   2-(R1-P(=X)(-R2)-O-),3-R3-PYRAZOLO(1,5-A)PYRIMIDINE   IN WHICH R1 IS ALKOXY OR ALKYL WITH 1 TO 6 CARBON ATOMS, R2 IS ALKYL OR ALKOXY WITH 1 TO 6 CARBON ATOMS OR PHENYL OR MONOALKYLAMINO OR DIALKYLAMINO WITH UP TO 6 CARBON ATOMS IN EACH ALKYL MOIETY, R3 IS HYDROGEN OR HALOGEN, AND X IS OXYGEN OR SULFUR.

United States Patent 3,840,541 O-PYRAZOLOPYRIMIDINE-(THION0)-PHOS- PHORIC-(PHOSPHONIC 0R PHOSPHINIC)- ACID ESTERS OR ESTER-AMIDES Reimer Ciilln, Wuppertal-Elberfeld, Ingeborg Hammann,

Cologne, and Giinter Unterstenhiifer, Opladen, Germany, assignors to Bayer Aktiengesellschaft No Drawing. Filed June 15, 1972, Ser. No. 263,075 Claims priority, application Germany, June 14, 1971, P 21 31 298.1 Int. Cl. C07d 57/16 US. Cl. 260-256.5 R 9 Claims ABSTRACT OF THE DISCLOSURE O-pyrazolopyrimidine (thiono) phosphoric (phosphonic or phosphinic)-acid esters or ester-amides of the general formula in which R is alkoxy or alkyl with 1 to 6 carbon atoms,

R is alkyl or alkoxy With 1 to 6 carbon atoms, or phenyl, or a monoalkylamino or dialkylamino group with up to 6 carbon atoms per alkyl moiety,

R is hydrogen or halogen, and

X is oxygen or sulfur,

which possess insecticidal, acaricidal and rodenticidal properties.

The present invention relates to and has for its objects the provision of particular new O-pyrazolopyrirnidine- (thiono) phosphoric (phosphonic or phosphinic) -acid esters or ester amides, i.e. (thiono) phosphoric, phosphonic or phosphinic acid esters or ester amides of (optionally 3-halo-substituted)-2-hydroxy-pyrazolo 1,5-a] pyrimidine, which possess insecticidal, acaricidal and rodenticidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects, acarids and rodents, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known from Belgian Patent Specification 676,802 and Netherlands Published Patent Application 6516907 that O-pyrazolopyrimidine (thiono) phosphoric-(phosphonic or phosphinic)-acid esters, for example 0,0- diethyl O (5,7 dimethylpyrazolo[1,5 a]pyrirnidin (2)yl)-thiono-phosphoric acid ester (Compound A) and 0,0-diethyl-O-(3-chloro- (Compound B) or -3-bromo- 5,7 dimethylpyrazolo-[1,5 a] pyrimidin(2)ylphosphoric acid ester (Compound C), display a pesticidal action, especially an insecticidal and acaricidal action.

The present invention provides O-pyrazolopyrimidine- (thono) phosphoric (phosphonic or phosphinic) -acid esters or ester-amides of the general formula "ice in which R is alkoxy or alkyl with 1 to 6 carbon atoms,

R is alkyl or alkoxy with 1 to 6 carbon atoms, or phenyl, or a monoalkylamino or dialkylamino group with up to 6 carbon atoms per alkyl moiety,

R is hydrogen or halogen, and

X is oxygen or sulfur.

Surprisingly, the compounds of the invention show a considerably higher insecticidal and acaricidal action than the previously known compounds of analogous structure and the same type of action. The substances according to the invention thus represent a genuine enrichment of the art.

Preferably, R is straight-chain or branched lower alkyl with 1 to 4 carbon atoms, such as methyl, ethyl, nor isopropyl, n-, sec.-, tert.- or iso-butyl, or straight-chain or branched lower alkoxy with 1 to 4 carbon atoms, for example methoxy, ethoxy, nor iso-propoxy or n-, sec.-, tert.- or iso-butoxy; R is such lower alkyl or alkoxy, or phenyl, or mono-lower alkylamino or di-lower alkylamino with up to 4 carbon atoms in each alkyl moiety, such as a monomethylamino, monoethylamino, mono isopropylamino, mono-n-propylarnino, mono n butylamino, mono-sec.- butylamino, mono-iso-butylamino, mono-tert.-butylamino, dimethylamino, di-ethylamino, di-n-propylamino, di-isopropylamino, di-n-butylamino, di-isobutylamino, di-tert.- butylamino, di-sec-butylamino, methyl-isopropylamino or like radical; R is hydrogen, chlorine or bromine.

As examples of (thiono)-phosphoric-(phosphonic or phosphinic)-acid esters or ester-amides of the formula (I) which can be used, the following may be mentioned individually: 0,0-dimethyl-, 0,0-diethyl-, QO-di-n-propyl-, 0,0-di-iso-propyl-, 0,0-di-n-butyl-, 0,0-di-iso-butyl-, 0,0-di-sec.-butyl-, 0,0-di-tert.-butyl-, O-methyl-O- ethyl-, O-methyl-O-n-propyl-, O-methyl-O-isopropyl-, O- methy1-O-n-butyl-, O-ethyl-O-n-propyl-, O-ethyl-O-isopropyl-, O-ethyl-O-n-butyl-, O-ethyl-O-tert.-butyl-, O-n-propyl-O-n-butyl-, O-iso-propyl-O-n-butylor O-iso-propyl-O- tert.-butylphosphoric acid ester and the corresponding thiono analogues, and also O-methyl-, O-ethyl-, O-n-propyl-, O-iso-propyl-, O-n-butyl-, O-sec.-butyl-, O-isobutyland O-tert.-butyl-methane-, -ethane-, -propane-, -butaneand -benzenc-phosphonic acid ester as well as dimethane-, diethane-, di-n-propane-, di-iso-propane-, di-n-butane-,

. di-iso-butane-, di-sec.-butane, di-tert.-butane-, methanebutaneand methane-benzene phosphinic acid-ester, also O,N-dimethyl, O-methyl-N-ethyl-, O-methyl-.N-n-propyl-, O-methyl-N-iso-propyl-, O-methyl-N-n-butyl-, O-methyl- N-sec.-butyl-, O-methyl-N-iso-butyl-, O-methyl-N-tert.- butyl-, O-ethyl-N-methyl-, O-ethyl-'N-ethyl-, O-ethyl-N-npropyl-, O ethyl N iso propyl-, O-ethyl-N-n-butyl-, O-ethyl-N-sec.-butyl-, O-ethyl-N-iso-butyl-, O-ethyl-N- tert.-butyl-, O-n-propyl-N-methyl-, O-n-propyl-N-ethyl-, O,N-di-n-propyl-, O-n-propyl-N-iso-propyl-, O-n-propyl- N-n-buty1-, O-n-propyl-N-sec.-buty1-, O-n-propyl-N-isobutyl, O-n-propyl-N-tert.-butyl-, O-iso-N-methyl-, O-isopropyl-N-ethyl, O iso propyl-N-n-propyl-, O,N-di-isopropyl-, O-iso-propyl N n butyl-, O-iso-propyl-N-isobutyl-, O-isopropyl-N-sec.-butyl-, O-iso-propyl N tart.- butyl-, O n butyl-N-methyl-, O-n-butyl-N-ethyl-, O-nbutyl-N-n-propyl-, O-n-butyl-N-iso-propy1-, O-n-butyl-N- iso-butyl-, O,N di n butyl-, O-n-butyl-N-tert.-butyl-, O-tert.-butyl-N-methyl-, O-tert. butyl N ethyl-, O-tert.- butyl-N-n-propyl-, O-tert.-butyl N iso-propyl-, O-sec.- butyl-N-ethyl-, O-sec.-butyl-N-n-propyl-, O-sec.-butyl-N- iso-propylor O-sec.-butyl-N-n-butyl-phosphoric acid ester amide, as well as the corresponding dialkylamino ester amide and their thiono analogue esters of 2-hydroxypyrazolo[1,5-a]pyrimidine or its 3-chloroor 3-bromo derivative.

3 The invention also provides a process for the production of an O-pyrazolopyrimidine-(thiono)-phosphoric-(phosphonic or phosphinic)-acid ester or ester-amide of the formula (I) in which a (thiono)-phosphoric-(phosphonic or phosphinic)-acid ester halide or ester-amide halide of the general formula in which R R and X have the above-mentioned meanings, and Hal is halogen, preferably chlorine or bromine,

is reacted with a 2-hydroxypyrazolopyrimidine derivative of the general formula (III) in which R has the above-mentioned meaning,

in the presence of an acid acceptor or in the form of the corresponding alkali metal, alkaline earth metal or ammonium salt.

If 0,0-diethyl-phosphoric acid ester chloride and 2-hydroxy-pyrazolo[1,5-a] pyrimidine are used as starting substances, the course of the reaction according to the invention can be represented by the following equation:

(IIa) (IIIa) The (thiono)-phosphoric-(phosphonic or phosphinic)- acid ester halides or ester-amide halides of the formula ('II) are known and are accessible in accordance with customary procedure. The 2-hydroxy-pyrazolo[1,5-a] pyrimidine derivatives of the formula (III) have hitherto not been described but can be prepared in accordance with methods which are in principle known. Thus, for example, the unsubstituted 2 hydroXy-pyrazolo[1,5-a] pyrimidine is obtained from a solution of 3-aminopyrazolone-(5) in ethanol and water, which has been saturated with HCl gas at 0 C., by reaction with 1,1,3,3-tetramethoxypropane. The products halogenated in the 3-position are obtained therefrom by halogenation.

The process of the invention is preferably carried out with the use of a solvent which term includes a mere dil-.

uent. As such it is possible to use practically all inert organic solvents. They include, above all, aliphatic and aromatic, optionally chloronated hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene; ethers, for example diethyl ether, dibutyl ether, dioxane; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone; nitriles, for example acetonitrile, propionitrile; and formamides, especially dimethyl-formamide.

As acid acceptors it is possible to use all customary acid binders. Alkali carbonates and alcoholates, such as sodium carbonate or potassium carbonate, sodium methylate or potassium methylate or sodium ethylate or potassium ethylate, as well as aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proved particularly suitable.

The reaction temperature can be varied over a wide range. In general, the reaction is carried out at from about 0 to 0., preferably about 15 to 35 C. The reaction is generally carried out at normal pressure.

For carrying out the process, the starting substances are in most cases employed in equimolar ratios. An excess of one or other reactant does not produce any significant advantages. The reaction is preferably carried out in the presence of one of the above-mentioned solvents and in the presence of an acid acceptor, at the temperatures indicated; after stirring for one or more hours at the indicated temperatures, the reaction mixture may be workedup by treating it with ice water. Thereupon, either the product already precipitates in solid form and is filtered off, washed and recrystallized if necessary, or the mixture is extracted with an organic solvent, preferably methylene chloride. After washing and drying the extract, the solvent is removed under reduced pressure and the oily residue is heated until slight distillation occurs.

The substances according to the invention are mostly obtained in a crystalline form and are characterized by their melting points. However, if they are obtained in the form of mostly yellowish-reddish oils, which cannot be distilled without decomposition, these may be freed of the remaining volatile constitutents by so-called slight distillation, that is to say prolonged heating under reduced pressure to moderately elevated temperatures, and may be purified in this way. In this case, their refractive indexes may be used to characterize them.

As has already been mentioned, the new O-pyrazolopyrimidine (thiono) phosphoric (phosphonic or phosphinic)-acid esters or ester-amides are distinguished by an excellent insecticidal and acaricidal activity against crop pests, hygiene pests and pests of stored products. They possess a good action against both sucking and biting insects and mites (Acarimz). At the same time they display only a slight phytotoxicity; they also display some rodenticidal action.

For these reasons, the products according to the invention may be successfully employed as pesticides in the protection of crops and stored products, and in the hygiene field.

To the sucking insects contemplated herein there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Mqgrosiphum solanifolii), the currant gall aphid (Cryptom'y zus-korschelti), the rosy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry blackfly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the Oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), such as Hercinothrips femoralis, and bugs, for example the beet bug (Piesma quadrara), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius prolz'xus) and Chagas bug (Triatoma infestants) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella 'p hey gypsy moth (Lymantrz'a dispar), the brown-tail moth (Euproctis chrysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (A grotis segetum) the large white butterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyworrn (Laphygma frugiperda) and cotton worm (Prodenz'a; litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kithniella) and; greater wax moth (Galleria mellonella'); and they lik Also to be classed with the biting insects contemplated herein are beetles (Coleoptera), for example the granary weevil (Sitophilus granarius=Calandra granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus), the raspberry beetle (Byturus tomentosus), the bean wevil (Bruchidius=Acanthoscelides obtectus), the leather beetle (Dermestes frischi), the khapra beetle (Trogoderma granarium), the flour beetle (Tribolium castaneum), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and the sawtoothed grain beetle (Oryzaephilus surinamensis), and also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such as the German cockroach (Blaltella germanica), American cockroach (Peripl aneta americana), Madeira cockroach (Leucophaea or Rhyparobia maderae), oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Acheta domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosophila melanogasfer), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannia canicularis), the black blow fly (Phormia regina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.

With the mites (Acarz') contemplated herein there are classed, in particular, the spider mites (Tetranychia'ae) such as the two-spotted spider mite (Tetranychus telarius =Tetranychus althaeae or Tetranychus urticae) and the European red mite (Paratetranychus pilosus=Panonychus ulmi), gall mites, for example the black current gall mite (Eriophyes rz'bis) and tarsonemids, for example the broad mite (Hemz'tarsonemus latus) and the cyclamen mite '(Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata); and the like.

When applied against hygiene pests and pests of stored products, particularly flies and mosquitoes, the compounds of the invention are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers, or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as Freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or Water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.) whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surfaceactive agents, for this purpose: emulsifying agents, such as non-ionic and/ or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/ or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/ or liquid dispersible carrier vehicles and/ or With other known compatible active agents, especially plant protection agents, such as other insecticides, acaricides, and rodenticides or fungicides, bactericides, nematocides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules Which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.195% by weight, and preferably 0.5% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10%, preferably 0.014%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-%, and preferably 0.01-95 by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, eg average particle diameter of from 50 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liter/hectare are needed, and often amounts only up to about 15 to 1000 g./hectare, preferably 40 to 600 g./hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects, acarids and rodents, and more particularly methods of combating at least one of insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, (c) such rodents, and (d) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally, acaricidally or rodenticidally effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, and the like.

. It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend uopn the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 A mixture of 99.0 g. (1 mole) of 3-aminopyrazolone, 750 ml. of ethanol and 100 ml. of concentrated hydrochloric acid is saturated with gaseous hydrogen chloride at C. Thereafter, 164.2 g. (1 mole) of 1,1,3,3-tetamethoxypropane are added dropwise to the mixture at an internal temperature of to 0 C. and the mixture is stirred for one hour without a cooling bath and for a further hour at 50 C.

The resulting yellow salt is filtered oil on a frit at 20 C. and is rinsed with ethanol and then dissolved in 1.2.1. of Water, and the solution is adjusted to a pH-value of 34 by adding sodium hydroxide solution. The product which has precipitated is filtered off, repeatedly rinsed with water and dried. In this way, 101.0 g. (74.2% of theory) of 2-hydroxy-pyrazolo[1,5-a]pyrirnidine are obtained in the form of a pale reddish powder of melting point 176 to 177 C.

(IIIa) 47.0 g. (0.25 mole) of 0,0-diethylthionophosphoric acid ester chloride are added dropwise while stirring to a mixture of 33.8 g. (0.25 mole) of 2-hydroxy-pyrazolo- [1,5-a]pyrimidine, 200 ml. of dimethylformamide and 35 g. of potassium carbonate, at an internal temperature of 30 C.; the reaction mixture is subsequently stirred for a further 2. hours at 30 C. and is then treated with 330 ml. of ice-cold water at below C., and the batch is twice extracted with 150 ml. of methylene chloride at a time. The combined extract is extracted by shaking three times with 200- ml. of water and the methylene chloride solution is dried over sodium sulfate. After removal of the solvent under reduced pressure and slight distillation of the residue, 54.9 g. (76.5% of theory) of 0,0-diethyl O (pyrazolo[1,5-a]pyrimidin(2)yl) thionophosphoric acid ester are obtained as a yellowish-reddish oil of refractive index n =1.5569.

EXAMPLE 2 H0 N (IIIb) 135.2 g. (1 mole) of 2-hydroxy-pyrazole[l,5-a]pyrimidine are dissolved in 1 l. of 1 N sodium hydroxide solution. 160 g. of bromine are added dropwise to this solution at an internal temperature of 40 to 50 C. while stirring, the mixture is subsequently stirred for a further hour at 50 C. and cooled to 20 C., and the reaction product is filtered oil and repeatedly washed with water. The product is then suspended in ethanol, again filtered off and washed with ethanol. After drying, 186 g. (87% of theory) of 2-hydroxy-3-bromo-pyrazolo[1,5-a] pyrimidine are obtained in the form of a yellowish powder which does not have a definite melting point but gradually chars above 200 C., with decomposition.

43.0 g. (0.25 mole) of O-ethyl-ethanethionophosphonic acid ester chloride are added dropwise while stirring to a mixture of 53.5 g. (0.25 mole) of 2-hydroxy-3-bromopyrazolo[l,5-a]pyrimidine, 200 ml. of dimethylformamide and 35 g. of potassium carbonate, at an internal temperature of 30 C.; the reaction mixture is stirred for a further 2 hours at 30 C., and 400 ml. of ice-cold water are then gradually added at below 10 C. Hereupon, the reaction product precipitates in a crystalline form and is filtered oif, repeatedly washed with water, covered with ligroin and dried. In this way, 72.1 g. (82.4% of theory) of yellowish crystals of melting point 63 to 64 C. are obtained. Recrystallization of these from 72 ml. of methanol yields 59.0 g. of O-ethyl-O-[3-bromo-pyrazolo[1,5-a]pyrimidin- (2)yl]-ethanethionophosphonic acid ester, analytically pure, in the form of pale yellowish crystals of melting point 6465 C.

EXAMPLE 3 43.0 g. (0.25 mole) of 0,0-diethylph0sphoric acid ester chloride are added dropwise at room temperature to a mixture of 33.8 g. (0.25 mole) of 2-hydroxypyrazolo- [1,5-a1pyrimidine, 150 ml. of dimethylformamide and 27.5 g. of triethylamine, while cooling externally and stirring; the reaction mixture is allowed to continue reacting for 2 hours at room temperature, 350 ml. of ice-cold water are subsequently slowly added at below 10 C., and the batch is extracted by shaking with 200 ml. of methylene chloride. The organic phase is shaken with ml. of water, dried and freed of the solvent under reduced pressure, and the residue is subjected to slight distillation. In this way, 6 2.0 g. (91.5% of theory) of 0,0-diethyl-O- (pyrazo1o[1,5-a]pyrimidin(2)yl)-phosphoric acid ester are obtained as a yellowish-reddish oil of refractive index n =1.5147.

EXAMPLE 4 A solution of 135.2 g. (1 mole) of 2-hydroxy-pyrazolo- [1,5-a] pyrimidine and 40 g. (1 mole) of sodium hydroxide in 800 ml. of water is added to a solution of 282 g. (1 mole) of Chloroamine T in 2 l. of water at an internal temperature of 5 to 15 70., while stirring and cooling externally. After the mixture has been stirred for 1 hour at 15 to 20 C., it is treated with 60. g. of glacial acetic acidjand after a further hour it is brought to a pH-value of exactly 9 and the p-toluenesulfonamide formed is filtered off and rinsed with water. 150 ml. of glacial acetic acid, are added to the filtrate. After stirringlfor 30 minutes, the reaction product is filtered 01f, thoroughly washed withwater, suspended in ethanoLagain filtered 011 and rinsed with ethanol. After drying, 147.8 (87% of theory) of 2-hydroxy-3-chloropyrazolo[LS-aJpyrimidine are obtained in the form of a reddish powder which does not have a definite melting point but gradually chars above 200 C., with decomposition.

(b) I N 36.2 g. (0.25 mole) of 0,0-dirnethylphosphoric acid ester chloride are added dropwise to a mixture of 42.4 g. (0.25 mole) of 2-hydroxy-3-chloropyrazolo[1,5-a]pyrimidine, 200 ml. of dimethylformamide and 26.5 g. triethylamine while stirring and cooling, at an internal temperatiure of 20 to 25 C.; the reaction mixture is allowed to continue reacting for 1 hour at 25 C. and 400 ml. of ice-cold water are then slowly added at below 10 C., whereupon the reaction product crystallizes out. It is filtered off, repeatedly rinsed with water, covered with ligroin and dried. In this way 49.3 g. of 0,0-di methyl-O- (3-chloropyrazolo[ 1,5-a] pyrimidin(2) yl -phosphoric acid ester are obtained in the form of yellowish crystals of melting point 113 to 114 C. The product can be rendered analytically pure by recrystallization from methanol (melting point 114 to 115 C.).

EXAMPLE The following compounds can be manufactured by methods analogous to those of Examples 1 to 4:

TABLE 1 Prepared analo- Melting rgusly to point Formula xample C.)

i 2 aO)2P-O N H (CHflOhP-O- \N/NM 7 N 2 75-76 Cl i (CHaOhP-O- N v i I (CH 0);PO- N/ v CgHr S C2H5 S CQHIO TABLE 1Continued Prepared analo- Melting gously to point Formula Example C.)

CiHsO S C2Hs0\fi L C2 s0 S I O3: PO- N C2H50 S CE: P-O N N N CH:

C2 s S CE: N

3 (CHahP-O-M it I (CHa)2PO N (18)..--. Br N 2 86-87 it I l a)2 \N/N (CHIMCHO S l 0 CH:

(CH|)2CHO S (CHrhCHO S l o N CH;

TABLE 1Continued Prepared analo- Melting gously to aim Formula Example C.)

(23) Br N 4 117-118 I? wmonn-o-k ll (C:H5O)zP-O N BP a 51-52 u (CzH O)gP-O- N 26 N cl 4 106-108 C2 s fi P-O \N/N 0 Ha) a C H-N P-O \N/N 0 Ha) 2 C H-NH EXAMPLE 6 Plutella test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound until dew moist and are then infested with caterpillars of the diamondback moth (Plutella maculipennis).

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the caterpillars are killed whereas 0% means that none of the caterpillars are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from Table 2:

TABLE 2Contlnued De ee Concenof fie tratlon 0t structlon I active in percompound cent after Active compound in percent 3 days (16)- N 0. 01 100 0. 001 100 i a)zP0 \N/N 6 I N 0 0903i i8" i 0. 0001 7 Q M -Q-KN 0 22) N\ .031 25 H 0.0001 70 (omonn-o \N/N (1)- N 0. 01 100 0.001 100 S (Cz 5 )2 N a N 0. 01 0 0.001 18" 0. 0001 0 (CzH5O)2P-O N (9)-...- 02H: N 0.01 100 \fi 0. 001 100 /P-o J CzHno N N 01 N\ 0903i i Ti 0. 0001 (CHa)zP--O N m N\ as: 138 S 0. 0001 90 ll 0.00001 00 (CHaO)2P-O N 0 000001 30 (5) N 0.01 Cl 0. 001 100 8 0.0001 97 ll 0. 00001 90 (CzHsO) 2PO N 0. 000001 00 (24)--.-- N 0. 01 100 01 0. 001 100 i (C2 5 )2 N 01H 01 N\\ 0903? i 000 100 l o N CzH O (1s N o. 01 100 Br 0. 001 100 3 0. 0001 80 (CHa)gP--O N (8) N o. 01 100 8 Br o. 001 100 II (CH1 )2 0 N 13 14 TABLE 2C0ntinued TABLE 3Continued Concen- Degree Concen- Degree tration of of detration oi oi deactive struction active struction compound in percompound in perin percent cent after in percent cent alter Active compound 3 days 5 Active compound day 25 0.01 100 G N 0.1 so N 0.001 100 Bi CH; 0.01 20 S B K 0.0001 100 i 0.001 0 ll (CzHaO): -O (cmionrw L \N/N (known) CH1 N 0 00i i% (c) N o 1 100 Br 0.0001 10 Br cm 0.01 90 C:H|\fi ll 0.001 0 P-o (c1mo),1 0L\ C1H|O N 0.001 100 (known) c1 cm CH0 3 (0) N 0.1 100 (p )1 {l OL J 20 S 0 1 1 g N 0. 0001 50 CH: (C x )I N 0 00i i% 22 N 0 1 100 B 25 0.01 100 (CHmCHO S O 0.001 85 i 0 (CH10) N m CH:

1 N 0.1 100 O 0.01 100 EXAMPLE 7 N 95 (C2Hs0)iP-0 Myzus test (contact act1on) normally sensitive N Solvent: 3 parts by weight acetone 13g Emulsifier: 1 part by weight alkylarylpolyglycol ether. H .0 1 95 To produce a suitable preparation of active compound, IH5O)2P-ON/ 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount (9). N 0.1 100 of emulsifier and the concentrate is diluted with water to 40 61H5 B 9 8} 33 the desired concentration. \ii 0 0.0001 00 Cabbage plants (Brassica oleracea) which have been M heavily infested with peach aphids (Myzus persicae) are CQHBO sprayed with the preparation of the active compound until N M 100 dripping wet. S 01 i 33 After the specified periods of time, the degree of de- H @88 struction is determined as a percentage: 100% means )1 that all the aphids are killed whereas 0% means that none of the aphids are killed. 5 /N 0.1 100 The active compounds, the concentrations of the active 50 3 C1 8: gg compounds, the evaluation times and the results can be H 0001 70 seen from the following Table 10 N 0.1 100 'rABLEs o1 0.01 100 [Myzus Test/normally sensitive] 01H; S 0. 001 100 \ll 0. 0001 40 Concen- Degree P-O N tration oi oi de- N active struction CaHsO vigmpound i111 apier- BIOBD. cen 81' Active compound 1 day Br (A) N\ CH .006} 88 (H) 0.001 95 n i 0.601 0 (C2HsO)1PO N (CzHsO)2P-O N V 2 N 0.1 100 \N O r 0.01 200 01111 S 0. 001 100 \II 0. 0001 00 own) (F)..... N 0.1 98 cflHlo o1 CH: 0. 01 40 s 0.001 0 (10 N 0.1 100 c H 0) i 0 (CH) CH0 5 0 08i i% 2 6 2 \N/N l 2 o HI \N/N 15 16 TABLE 3Continued TABLE 4-Continued C D t traiiiffir o i d Concen- D331? active struction tration of struction compound peractive in perin percent cent after compound cent after A v compound y 5 Active compound in percent 2 days (20 N 0.1 100 a I r 01 0.01 100 (known) N M 0 (CHa):CHO\fi l I 0.001 98 \N/N g 1() (CzHs0)zP O \N/N 21 N 0.1 100 Br 0.01 100 (C Ha) zCHO\fi O. 001 98 (known) PO\ N (o)- N Q 7 0.1 0

N/ on. Q i CH1 0%: meat-O W CIHBO 0 o. 001 75 I o CH: K N

N/ (CHahCH-Nfi (kmwn) 1 Br- (L1H: EXAMPLE 8 Tetranychus test/resistant o 0 H Solvent: 3 parts by weight acetone 2 7 0H, Emulsifier: 1 part by weight alkylaryl polyglycol ether. (known) 7 To produce a suitable preparation of active compound, N 0 1 g 1 part by weight of the active compound is mixed with S m 85 the stated amount of solvent containing the stated amount (CH) {1 of emulsifier and the concentrate so obtained is diluted with water to the desired concentration. 1

Bean plants (Phaseolus vulgarz's), which have a height (6) 1% of approximately 10-30 cm., are sprayed with the prefi 0.001 90 paration of the active compound until dripping wet. CH O) These bean plants are heavily infested with spider mltes a a N (Tetranychus urticae) in all stages of development. (22) N 0 1 100 After the specified periods of time, the eflectiveness M 100 of the preparation of active compound is determined by 40 H counting the dead mites. The degree of destruction thus N obtained is expressed as a percentage: 100% means that all the spider mites are killed Whereas 0% means that (1) N OJ m0 none of the spider mites are killed. 0. 01 100 The active compounds, the concentrations of the active fi 95 compounds, the evaluation times and the results can be c,H,o 2P-o IN seen from the following Table 4: N

(a) N 0.1 100 TABLE 4 0.01 100 [Tetranychus test/resistant] 001 Degree (CzH5o)aP o I t i 333;

ra 1on v N .1 1 0 active in per- (9) 3,11, 0901 180 compound cent after 5 001 50 Active compound in percent 2 days 13 N 0.1 0 55 s canto ll (17 N 0.1 100 (Carma-0 c1 0.01 100 N i 0. 001 so on, onmP-o IN (known) (7) N 0.1 100 (E)......' 1 0.1 0 c1 0.01 100 CH 8 cm i 0. 001

5 (CH10)zP-O N P-O N/ \N/N 0,1150 (4) N 0.1 100 0m 01 0. 01 0. 001 30 (CHaO) P-O n) N 0.1 a 0 70 N Cl CH: s (5) N 0.1 ll 1 0. 01 100 0.001 99 Degree Coneenof detration of struetion active in percompound cent after Active compound in percent 3 days O I! 2 5 )fl \N/N\/ N 0.1 100 o1- 0. 01 100 L J 0.001 95 0 H; S H P0 N C2H5O N 0.1 100 Br- 0.01 100 J 0. 001 45 S ll onmP-o N N 0.1 100 (8) Br 0. 01 100 g 0.001 100 (CHaO)2PO N N 0.1 100 Br- 0.01 100 C2H5 3 0.001 75 1 -0- \N/N CHiO 0%: i0 (CHa)2CHO\fi 0.001 00 /PO- \N/N CHO 0.1 100 a N\ 10 (CHahCHO fi 0.0001 50 EXAMPLE 9 Myzus test (contact action/resistant) Solvent: 3 parts by weight acetone Emulsifier: '1 part by weight alkylarylpolyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the aphids are killed whereas 0% means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 5:

TABLE 5 [Myzus persicae test/resistant] D Concen- 02 Active compound tration of struction active in percompound cent after in percent 1 day (D) 0H: 0.1 00 0. 02 a0 N--N l fi/O C2115 CH3 O-P OCzHs (known) (G) CH0 0.1 0

fi/O 0211:

I 001115 Br (known) m N 0.1 100 0. 02 50 i (CzH5O)zP-O \N/N 0.1 100 (9) /N\ 0.02 100 02115 i i 0.004

P-O \N/N 02115 C2H5O .1 100 (2) N\ 0902 100 mm s Brl 0. 004 80 N/ CzH5O EXAMPLE l0 Phorodon test (contact action/resistant) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Hop plants (H umulus lupulus) which have been heavily infested with the hop aphid (Phorodon humuli) resistant, are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the aphids were killed; 0% means that none of the aphids were killed.

19 The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 6:

TABLE 6 [Phorodon humuli test/resistant] Degree Concenof detration of struction active in percompound cent after Active compound in percent 1 day (G) CH 0.1 75 $082 Z8 S 00211 H {V C a N l OC2H Br (known) (1) N 0. 1 100 0.02 100 S 0. 004 90 ll 0.0008 20 (CzH5 )2P--0 N (9) N 0. 1 100 0.02 100 C2H5 S 0. 004 100 \ll 0 0.0008 85 N CZH O (10 N 0. 1 100 1 0. 02 100 (32115 S O. 004 100 0.0008 75 P O CzHa 2 N 0. 1 100 Br 0. 02 100 C2Hs S 0. 004 100 II 0 0008 40 CZHB It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

1. An O-pyrazolopyrimidine (thiono) phosphoric- (phosphonic or phosphinic)-acid ester of the formula in which R is alkoxy or alkyl with 1 to 6 carbon atoms,

R is alkyl or alkoxy with 1 to 6 carbon atoms or phenyl or monoalkylamino or dialkylamino with up to 6 carbon atoms in each alkyl moiety,

R is hydrogen or halogen, and

X is oxygen or sulfur.

2. A compound according to claim 1 in which R is lower alkyl or alkoxy, R is lower alkyl or alkoxy, phenyl, mono-lower alkylamino or di-lower alkylamino, and R is hydrogen, chlori e o bromi e.

3. The compound according to claim 1 wherein such compound is O ethyl O [3-bromo-pyrazolo[1,5-a] pyrimidin(2)yl] -ethanethionophosphonic acid ester of the formula 02115 S ll C2H5O 4. The compound according to claim 1 wherein such compound is 0,0 diethyl O-[3-chloro-pyrazolo[1,5-a] pyrimidin(2)yl]-thionophosphoric acid ester of the formula 5. The compound according to claim 1 wherein such compound is O ethyl O (pyrazolo[l,5-a]pyrimidin (2)yl)-ethanethionophosphonic acid ester of the formula \l] /PO \N/N\/ 6. The compound according to claim 1 wherein such compound is O ethyl O [3 chloro-pyrazolo[l,5-a] pyrimidin(2)yl] -ethanethionophosphonic acid ester of the formula l 0 l s 7. The compound according to claim 1 wherein such compound is O-isopropyl O [3-chloro-pyrazolo[l,5-a] pyrimidin(2)yl]-methanethionophosphonic acid ester of the formula 8. The compound according to claim 1 wherein such compound is O isopropyl O-[3-bromo-pyrazolo[1,5-a]

pyrimidin(2)yl]-methanethionophosphonic acid ester of the formula 9. The compound according to claim 1' wherein such compound is 0,0 diethyl O-[3-bromo-pyrazolo[1,5-a] pyrimidin(2)yl]-phosphoric acid ester of the formula RICHARD J. GALLAGHER, Primary Examiner UNHLD S'lA'l'ES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3.840.541 Dated October a, 1974. Inventofls) Reimer caun et al. (Page 1 of 2 It is certified that error appears' in the always-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 1, line 9, cancel priority date of "June 1 1971." and i substitute June 24, 'l97l Col. 1 line 64, cancel "(tnonoY and substitute (thiono) Col; 4, line 59, correct: spelling of "infestans".

. Col. 4 line 65, cancel "they" and substitute the Col. 7, Compound (1), correct formula to read as follows:

Col. 8, line 66, at left-hand side column, insert (a) Col. 10, line 66, cancel "94-99" and substitute 94-95 Col. 12, Table 2, Compound (9), correct formula to read as N follows: 0.11.

P O N o 01110 Col. 14, Table 3,Compound (G) correct formula to read as follows UNl'l'lSD SL'A'USS PA'L'EN'I 01mm; CERTIFICATE OF CORRECTION Parent no. 3,840,541 Dated October 8, 1974 Invsmofls) (Page 2 of 2) It is certified that: error appearsdn the aboye-idcncified patent and that said Letters Patent are hereby corrected as shown below:

Col. l4 Table 3, Compound (2) in lasc column of Table,

cancel "-200" and substitute 100 Col 15, line 5, Table 3 heading of last column, cancel 3 days" and substitute 1 day I Col. 17, line 4, Table 4, in tbe heading-of the last column,

cancel 3 days" and substitute 2 days Col. 17, Table 4, Compound (2 correct formula to read as follows 2 Dr N\ n I /P-01\N/N Signed and sealed this 15th day of July 1975.

(SEAL) Attest;

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks 

1. AN O-PYRAZOLOPYRIMIDINE - (THIONO) - PHOSPHORIC(PHOSPHONIC OR PHOSPINIC)-ACID ESTER OF THE FORMULA 